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FR2902434A1 - Polylactic composition, useful e.g. to make molded-, extruded- and thermoformed articles, comprises polylactic acid, ethylene copolymer e.g. ethylene-methylacrylate-glycidyl methacrylate and ethylene-alkyl(meth)acrylate copolymer - Google Patents

Polylactic composition, useful e.g. to make molded-, extruded- and thermoformed articles, comprises polylactic acid, ethylene copolymer e.g. ethylene-methylacrylate-glycidyl methacrylate and ethylene-alkyl(meth)acrylate copolymer Download PDF

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Publication number
FR2902434A1
FR2902434A1 FR0652160A FR0652160A FR2902434A1 FR 2902434 A1 FR2902434 A1 FR 2902434A1 FR 0652160 A FR0652160 A FR 0652160A FR 0652160 A FR0652160 A FR 0652160A FR 2902434 A1 FR2902434 A1 FR 2902434A1
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France
Prior art keywords
ethylene
copolymer
meth
acrylate
alkyl
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Granted
Application number
FR0652160A
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French (fr)
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FR2902434B1 (en
Inventor
Thomas Fine
Maliha Khusrawy
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Arkema France SA
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Arkema France SA
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Priority to FR0652160A priority Critical patent/FR2902434B1/en
Application filed by Arkema France SA filed Critical Arkema France SA
Priority to PL07788972T priority patent/PL2032649T3/en
Priority to KR1020087030609A priority patent/KR101332990B1/en
Priority to ES07788972T priority patent/ES2368093T3/en
Priority to CN2007800279732A priority patent/CN101495568B/en
Priority to US12/305,127 priority patent/US9512311B2/en
Priority to DK07788972.3T priority patent/DK2032649T3/en
Priority to EP07788972A priority patent/EP2032649B1/en
Priority to PCT/FR2007/051403 priority patent/WO2007144529A1/en
Priority to AT07788972T priority patent/ATE518912T1/en
Priority to JP2009514857A priority patent/JP5174017B2/en
Publication of FR2902434A1 publication Critical patent/FR2902434A1/en
Application granted granted Critical
Publication of FR2902434B1 publication Critical patent/FR2902434B1/en
Expired - Fee Related legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/361—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die with the barrel or with a part thereof rotating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0884—Epoxide-containing esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31736—Next to polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Polylactic composition comprises polylactic acid (PLA) at 60-97 wt.% and a polymer mixture at 3-40 wt.%. The polymer mixtures comprises a copolymer (I) of ethylene and an unsaturated monomer with epoxy, carboxylic acid or its anhydride units and optionally alkyl(meth)acrylate, and an ethylene-alkyl(meth)acrylate copolymer (II). The weight ratio of (I) to the sum of (I) and (II) is 0.1:0.49. Independent claims are included for: (1) a process of preparing the composition comprising extruding the PLA with the polymer mixture; (2) a part/article obtained by molding, extruding and thermoforming the composition; and (3) a multi-layer structure comprising a layer made up of the composition, and at least a layer made up of thermoplastic e.g. polyethylene, polypropylene, polystyrene, polyamide or and ethylenevinyl alcohol copolymer.

Description

Composition d'acide polylactique présentant une résistance aux chocsPolylactic acid composition with impact resistance

améliorée. Domaine technique : La présente invention concerne une composition d'acide polylactique 5 présentant une résistance aux chocs améliorée. Technique antérieure : L'acide polylactique (PLA) est un polyester synthétisé à partir d'un monomère d'origine végétale. En raison de ses propriétés biodégradables et renouvelables, il présente un intérêt majeur. Toutefois, il s'agit d'un polymère lo particulièrement fragile qui nécessite un renforcement aux chocs. Dans l'état actuel de la technique, JP H09-316310 décrit des compositions de PLA renfermant des copolymères éthylène-méthacrylate de glycidyle greffés avec du polystyrène ou du polydiméthacrylate ou encore, des polyoléfines greffées avec l'anhydride maléique. 15 Plus récemment, WO 2005/059031 décrit des résines PLA modifiées à l'impact par un mélange contenant au moins 50% d'un copolymère éthylène-(méth)acrylate d'alkyle-(meth)acrylate de glycidyle avec un copolymère éthylène-(méth)acrylate d'alkyle. Ces compositions présentent certes une résistance aux chocs améliorée, 20 toutefois, cette résistance n'est pas encore entièrement satisfaisante, notamment à basse température. D'autre part, ces compositions présentent une fluidité nettement inférieure à celle du PLA. Cette baisse importante de fluidité est nuisible à la mise en oeuvre, tout particulièrement pour les pièces injectées fines et de grande 25 dimension. Le but de la présente invention est de proposer une composition de PLA qui présente à la fois une bonne résistance aux chocs, notamment à basse température, et une bonne fluidité. Exposé de l'invention : 30 La présente invention concerne une composition d'acide polylactique comprenant en poids : - 60 à 97 % d'acide polylactique (PLA) et, - 3 à 40 % d'un mélange de composés A et B dans lequel, o A est un copolymère d'éthylène et d'un monomère insaturé porteur d'au moins une fonction époxyde ou acide carboxylique ou anhydride d'acide carboxylique, et éventuellement de (méth)acrylate d'alkyle. o B est un copolymère d'éthylène et de (méth)acrylate d'alkyle, ledit mélange présentant un rapport % poids (A) / % poids (A +B) compris entre 0,10 et 0,49. lo La demanderesse a découvert de façon surprenante que des compositions de PLA renfermant majoritairement du copolymère éthylène-(méth)acrylate d'alkyle dans le mélange A + B confèrent, aux pièces obtenues à partir de ces compositions, une résistance aux chocs améliorée, à température ambiante et tout particulièrement à froid. Cette résistance aux chocs est 15 supérieure à celle des compositions riches en copolymère éthylène-(méth)acrylate d'alkyle-(méth)acrylate de glycidyle. En outre, ces compositions présentent un bon compromis entre la résistance aux chocs et la viscosité. Selon une variante de l'invention, le composé A est un copolymère de 20 l'éthylène et d'un époxyde insaturé qui peut être obtenu par copolymérisation de l'éthylène et d'un époxyde insaturé ou par greffage de l'époxyde insaturé sur le polyéthylène. Le greffage peut être effectué en phase solvant ou sur le polyéthylène en fusion en présence d'un péroxyde. Ces techniques de greffage sont connues en elles-mêmes. Quant à la copolymérisation de l'éthylène et d'un 25 époxyde insaturé, on peut utiliser les procédés dits de polymérisation radicalaire fonctionnant habituellement à des pressions entre 200 et 2 500 bars. A titre d'exemple d'époxydes insaturés, on peut citer : - les esters et éthers de glycidyle aliphatiques tels que l'allylglycidyléther, le vinyl glycidyléther, le maléate et l'itaconate de glycidyle, le 30 (méth)acrylate de glycidyle, et, - les esters et éthers de gycidyle alicycliques tels que le 2-cyclohexène-1-glycidyléther, le cyclohexène-4,5-diglycidyl carboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2glycidyl carboxylate et l'endo cis-bicyclo(2,2,1)-5-heptène-2,3-diglycidyl dicarboxylate. Le copolymère d'éthylène et d'époxyde insaturé peut comprendre aussi d'autres monomères pouvant être choisis par exemple parmi : - les alphaoléfines telles que le propylène, le butène-1, l'hexène... -les esters vinyliques d'acides carboxyliques saturés tels que l'acétate de vinyle ou le propionate de vinyle - les esters d'acide carboxyliques saturés tels que les lo (méth)acrylates d'alkyle pouvant avoir jusqu'à 24 carbones. A titre d'exemple on peut greffer l'époxyde insaturé sur les polymères suivants : - le polyéthylène, les copolymères de l'éthylène et d'une alphaoléfine, les polyéthylènes tels que le VLDPE (PE très basse densité), le 15 ULDPE (PE ultra basse densité) ou le PE métallocène ; les copolymères de l'éthylène et au moins un ester vinylique d'acide carboxylique saturé tel que l'acétate de vinyle ou le propionate de vinyle - les copolymères de l'éthylène et d'au moins un ester d'acide carboxylique insaturé, tels que les (méth)acrylates d'alkyle pouvant avoir jusqu'à 20 24 carbones ; - les élastomères EPR (éthylène/propylène rubber) ou les EPDM (éthylène/propylène/diène) ; - des mélanges de polymères choisis parmi les précédents. Le composé A de l'invention est avantageusement un copolymère 25 éthylène/(méth)acrylate d'alkyle/époxyde insaturé. Avantageusement il peut contenir jusqu'à 40 % en poids de (méth)acrylate d'alkyle. L'époxyde est avantageusement le (méth)acrylate de glycidyle. Avantageusement le (méth)acrylate d'alkyle est choisi parmi le 30 (méth)acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de n-octyle et l'acrylate de 2-éthylhexyle La quantité de (méth)acrylate d'alkyle est avantageusement de 20 à 35 %.  improved. Technical Field: The present invention relates to a polylactic acid composition having improved impact resistance. Prior Art: Polylactic acid (PLA) is a polyester synthesized from a monomer of plant origin. Due to its biodegradable and renewable properties, it is of major interest. However, it is a particularly fragile polymer which requires impact reinforcement. In the present state of the art, JP H09-316310 describes PLA compositions containing ethylene-glycidyl methacrylate copolymers grafted with polystyrene or polydimethacrylate or else polyolefins grafted with maleic anhydride. More recently, WO 2005/059031 discloses impact-modified PLA resins with a mixture containing at least 50% of an ethylene-alkyl (meth) acrylate-glycidyl (meth) acrylate copolymer with an ethylene-ethylenediamine copolymer. alkyl (meth) acrylate. These compositions certainly have improved impact resistance, however, this resistance is not yet entirely satisfactory, especially at low temperature. On the other hand, these compositions have a fluidity significantly lower than that of PLA. This significant drop in fluidity is detrimental to the implementation, especially for fine and large sized injected parts. The object of the present invention is to provide a PLA composition which has both good impact resistance, especially at low temperature, and good fluidity. SUMMARY OF THE INVENTION The present invention relates to a polylactic acid composition comprising by weight: 60 to 97% polylactic acid (PLA) and 3 to 40% of a mixture of compounds A and B in wherein A is a copolymer of ethylene and an unsaturated monomer bearing at least one epoxide or carboxylic acid or carboxylic acid anhydride function, and optionally alkyl (meth) acrylate. B is a copolymer of ethylene and alkyl (meth) acrylate, said mixture having a ratio by weight (A) /% by weight (A + B) of between 0.10 and 0.49. The Applicant has surprisingly discovered that PLA compositions containing predominantly ethylene-alkyl (meth) acrylate copolymer in the A + B mixture impart to the parts obtained from these compositions, an improved impact strength, ambient temperature and especially cold. This impact resistance is superior to that of ethylene- (meth) acrylate-glycidyl (meth) acrylate-rich copolymer-rich compositions. In addition, these compositions have a good compromise between the impact resistance and the viscosity. According to a variant of the invention, the compound A is a copolymer of ethylene and an unsaturated epoxide which can be obtained by copolymerization of ethylene and an unsaturated epoxide or by grafting the unsaturated epoxide on polyethylene. The grafting may be carried out in the solvent phase or on the molten polyethylene in the presence of a peroxide. These grafting techniques are known per se. As for the copolymerization of ethylene and an unsaturated epoxide, the so-called radical polymerization processes, usually operating at pressures between 200 and 2500 bar, may be used. As examples of unsaturated epoxides, mention may be made of: aliphatic glycidyl esters and ethers, such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, and glycidyl (meth) acrylate, and alicyclic gycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate. The copolymer of ethylene and unsaturated epoxide may also comprise other monomers which may be chosen, for example, from: - alphaolefins such as propylene, butene-1, hexene, etc. - vinyl esters of acids saturated carboxylic acids such as vinyl acetate or vinyl propionate; saturated carboxylic acid esters such as alkyl lo (meth) acrylates having up to 24 carbons. By way of example, the unsaturated epoxide can be grafted onto the following polymers: polyethylene, copolymers of ethylene and of an alphaolefin, polyethylenes such as VLDPE (very low density PE), ULDPE ( Ultra-low density PE) or metallocene PE; copolymers of ethylene and at least one saturated carboxylic acid vinyl ester such as vinyl acetate or vinyl propionate; copolymers of ethylene and at least one unsaturated carboxylic acid ester, such as that the alkyl (meth) acrylates may have up to 24 carbons; elastomers EPR (ethylene / propylene rubber) or EPDM (ethylene / propylene / diene); mixtures of polymers chosen from the preceding ones. Compound A of the invention is preferably an ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymer. Advantageously, it may contain up to 40% by weight of alkyl (meth) acrylate. The epoxide is advantageously glycidyl (meth) acrylate. Advantageously, the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and n-octyl acrylate. and 2-ethylhexyl acrylate The amount of alkyl (meth) acrylate is preferably from 20 to 35%.

L'indice de fluidité ou MFI (MFI ou Melt Flow Index qui désigne l'indice d'écoulement à l'état fondu) de A est avantageusement compris entre 2 et 40 et de préférence de 5 à 20 (190 C - 2,16 kg). Ce copolymère peut être obtenu par polymérisation radicalaire des 5 monomères. Selon une autre variante, le composé A est un copolymère de l'éthylène et d'un anhydride d'acide carboxylique insaturé. A est soit un copolymère de l'éthylène et d'un anhydride d'acide carboxylique insaturé soit une polyoléfine greffée par un anhydride d'acide lo carboxylique insaturé. La polyoléfine peut être choisie parmi les polyoléfines pouvant être greffées par un époxyde insaturé citées plus haut. Des exemples d'anhydrides d'acide dicarboxylique insaturé utilisables comme constituants de A sont notamment l'anhydride maléique, l'anhydride 15 itaconique, l'anhydride citraconique, l'anhydride tétrahydrophtalique. A titre d'exemple, on peut citer les copolymères de l'éthylène d'un (méth)acrylate d'alkyle, d'un anhydride d'acide carboxylique insaturé et les copolymères de l'éthylène, d'un ester vinylique d'acide carboxylique saturé et d'un anhydride d'acide carboxylique insaturé. 20 La quantité d'anhydride carboxylique insaturé peut être jusqu'à 15 % en poids du copolymère et la quantité d'éthylène d'au moins 50 % en poids. Avantageusement A est un copolymère de l'éthylène, d'un (méth)acrylate d'alkyle et d'un anhydride carboxylique insaturé. De préférence le (méth)acrylate d'alkyle est tel que l'alkyle possède 2 à 10 atomes de carbone. 25 Le (méth)acrylate d'alkyle peut être choisi parmi ceux cités plus haut. Le MFI de A peut être par exemple entre 0,1 et 50 (g/10 mn à 190 C sous 2,16 kg). Selon l'invention, le composé B est un copolymère de l'éthylène et d'un (méth)acrylate d'alkyle. Le (méth)acrylate d'alkyle peut être choisi 30 avantageusement parmi le (méth)acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de n-octyle et l'acrylate de 2-éthylhexyle. La quantité de (méth)acrylate d'alkyle est avantageusement de 20 à 40 %.  The Melt Flow Index (MFI) of A is advantageously between 2 and 40 and preferably from 5 to 20 (190 C - 2.16). kg). This copolymer can be obtained by radical polymerization of the monomers. According to another variant, the compound A is a copolymer of ethylene and an unsaturated carboxylic acid anhydride. A is either a copolymer of ethylene and an unsaturated carboxylic acid anhydride or a polyolefin grafted with an unsaturated carboxylic acid anhydride. The polyolefin may be chosen from the unsaturated epoxy-grafted polyolefins mentioned above. Examples of unsaturated dicarboxylic acid anhydrides useful as components of A include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride. By way of example, mention may be made of ethylene copolymers of an alkyl (meth) acrylate, of an unsaturated carboxylic acid anhydride and copolymers of ethylene, of a vinyl ester of saturated carboxylic acid and an unsaturated carboxylic acid anhydride. The amount of unsaturated carboxylic anhydride may be up to 15% by weight of the copolymer and the amount of ethylene of at least 50% by weight. Advantageously A is a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated carboxylic anhydride. Preferably the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms. The alkyl (meth) acrylate may be selected from those mentioned above. The MFI of A can be for example between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg). According to the invention, compound B is a copolymer of ethylene and an alkyl (meth) acrylate. The alkyl (meth) acrylate may be advantageously selected from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl acrylate and the like. octyl and 2-ethylhexyl acrylate. The amount of alkyl (meth) acrylate is advantageously from 20 to 40%.

Selon un premier aspect de l'invention, la composition présente un rapport % poids (A)/ % poids (A +B) du mélange compris entre 0,15 et 0,40, et préférentiellement entre 0,20 et 0,30. La présente invention concerne également un procédé de préparation par 5 extrusion des compositions mentionnées ci-dessus. On peut opérer selon deux modes de réalisation particuliers : - Par mélange simultané du PLA, de A et de B ou, - Par la réalisation successive des deux étapes suivantes : a) le mélange de A et B, puis, l0 b) le mélange du produit issu de a) avec le PLA. En outre, l'invention se rapporte à l'utilisation de ces compositions ainsi qu'à des pièces ou objets fabriqués à partir de telles compositions. A titre non limitatif, on peut citer la fabrication de pièces moulées par injection, de films et feuilles extrudés et éventuellement thermoformés, de corps 15 creux mis en forme par extrusion soufflage, de récipients tels que des barquettes... Les pièces ou objets ainsi obtenus peuvent subir une étape de recuit. L'invention concerne également une structure multicouche comprenant une couche de la composition correspondant à l'invention et au moins une 20 couche d'un thermoplastique choisi parmi le polyéthylène (PE), le polypropylène (PP), le polystyrène (PS), le polyamide (PA) et le copolymère éthylène / alcool vinylique (EVOH). La présente invention va être maintenant illustrée par des exemples particuliers de réalisation qui vont être décrits ci-après. Il est précisé que ces 25 exemples ne visent en aucun cas à limiter la portée de la présente invention.  According to a first aspect of the invention, the composition has a ratio by weight (A) /% by weight (A + B) of the mixture of between 0.15 and 0.40, and preferably between 0.20 and 0.30. The present invention also relates to a process for the extrusion preparation of the compositions mentioned above. It is possible to operate according to two particular embodiments: by simultaneous mixing of the PLA, A and B or by the following realization of the two following stages: a) the mixture of A and B, then, 10 b) the mixture the product from a) with PLA. In addition, the invention relates to the use of these compositions as well as parts or objects made from such compositions. Non-limiting examples include the manufacture of injection-molded parts, extruded and possibly thermoformed films and sheets, hollow bodies shaped by extrusion blow molding, containers such as trays, etc. Parts or objects thus obtained can undergo an annealing step. The invention also relates to a multilayer structure comprising a layer of the composition corresponding to the invention and at least one layer of a thermoplastic chosen from polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA) and the ethylene / vinyl alcohol copolymer (EVOH). The present invention will now be illustrated by particular embodiments which will be described below. It is pointed out that these examples are in no way intended to limit the scope of the present invention.

Exemples :Examples:

Matières utilisées : 30 L'acide polylactique ou PLA est commercialisé par Natureworks, sous la référence PLA 2002D. Le composé A utilisé est un terpolymère d'éthylène (68 % pondéral), d'acrylate de Méthyle (AMe) (24 % pondéral) et de méthacrylate de glycidyle (GMA)(8 % pondéral), ayant un MFI égal à 6. Ce terpolymère est commercialisé par Arkema France, sous la référence Lotader AX8900. Le composé B utilisé est un copolymère d'éthylène (70% pondéral) et de butylacrylate (30% pondéral), ayant un MFI compris entre 1,5 et 2,5. Ce copolymère est commercialisé par Arkema France sous la référence Lotryl 30BA02. Caractéristiques des compositions testées : o Composition de référence : Essai 1 : 100%PLA o Compositions à titre comparatif : Essais 2 et 6 à 8 Essai 2 : 80% PLA +20% B Essai 6 : 80% PLA +10% A+10% B, soit %A/%(A+B)=0,5 Essai 7 : 80% PLA + 15% A+5% B, %A/%(A+B)=0,75 Essai 8 : 80% PLA + 20% A+5% B, %A/%(A+B)=1 o Compositions selon l'invention : Essais 3 à 5 Essai 3 : 80% PLA +2% A+18% B, soit %A/%(A+B)=0,1 Essai 4 : 80% PLA +4% A+16% B, soit %A/%(A+B)=0,2 Essai 5 : 80% PLA +6% A+14% B, soit %A/%(A+B)=0,3 Mode de préparation des différentes compositions : - Compoundaqe : Les compositions sont obtenues par compoundage sur une extrudeuse double vis L/D 30 munie d'un système de dégazage et d'une coupe à jonc, avec un débit de 15kg et une vitesse de vis de 280tr/min. Le profil de température utilisé est un profil de température croissant allant de 170 C à 200 C. La température matière est de 220 C: Avant le compoundage, le PLA a été séché pendant 4h à 70 C. -Moulaqe des échantillons : Les granulés sont séchés puis moulés sur une presse à injecter type dans les conditions suivantes : Température fourreau : 180/200 C Température moule : 30 C Pression d'injection : 1200 bar Pression de maintien : 700 bar Les éprouvettes normalisées (80 x 10 x 4mm3) ainsi obtenues sont recuites 30min à 100 C sous légère charge. Evaluation des compositions: - Résistance aux chocs sur des éprouvettes préalablement entaillées du 5 type Charpy selon la norme ISO 179 93 1 Ae à 23 C et -40 C. - Indice de fluidité (MFI) mesuré selon la norme ISO 1133-1981-F à une température de 190 C et sous un poids de 2,16kg. Les résultats des essais sont récapitulés dans le tableau 1 ci-après.  Materials used: Polylactic acid or PLA is marketed by Natureworks under the reference PLA 2002D. The compound A used is a terpolymer of ethylene (68% by weight), of methyl acrylate (AMe) (24% by weight) and of glycidyl methacrylate (GMA) (8% by weight), having an MFI equal to 6. This terpolymer is marketed by Arkema France, under the reference Lotader AX8900. The compound B used is a copolymer of ethylene (70% by weight) and butyl acrylate (30% by weight), having an MFI between 1.5 and 2.5. This copolymer is sold by Arkema France under the reference Lotryl 30BA02. Characteristics of the compositions tested: o Reference composition: Test 1: 100% PLA o Compositions for comparison: Tests 2 and 6 to 8 Test 2: 80% PLA + 20% B Test 6: 80% PLA + 10% A + 10 % B, ie% A /% (A + B) = 0.5 Test 7: 80% PLA + 15% A + 5% B,% A /% (A + B) = 0.75 Test 8: 80% PLA + 20% A + 5% B,% A /% (A + B) = 1 o Compositions according to the invention: Tests 3 to 5 Test 3: 80% PLA + 2% A + 18% B, ie% A /% (A + B) = 0.1 Test 4: 80% PLA + 4% A + 16% B, ie% A /% (A + B) = 0.2 Test 5: 80% PLA + 6% A + 14% B, ie% A /% (A + B) = 0.3 Method of preparation of the various compositions: Compoundaqe: The compositions are obtained by compounding on an L / D 30 twin-screw extruder equipped with a coating system. degassing and rake cutting, with a flow rate of 15kg and a screw speed of 280rpm. The temperature profile used is an increasing temperature profile ranging from 170 C to 200 C. The material temperature is 220 C: Before compounding, the PLA was dried for 4 hours at 70 ° C. -Moulaqe samples: The granules are dried and then molded on a typical injection molding machine under the following conditions: Sleeve temperature: 180/200 C Mold temperature: 30 C Injection pressure: 1200 bar Holding pressure: 700 bar Standard test specimens (80 x 10 x 4mm3) and obtained are annealed 30 min at 100 C under light load. Evaluation of the compositions: Impact strength on pre-cut samples of the Charpy type according to the ISO 179 93 1 Ae standard at 23 ° C. and -40 ° C. - Melt index (MFI) measured according to the ISO 1133-1981-F standard at a temperature of 190 C and under a weight of 2.16 kg. The results of the tests are summarized in Table 1 below.

lo Tableau 1 Essai 1 2 3 4 5 6 7 8 (réf) (comp.) (inv.) (inv.) (inv.) (comp.) (comp.) (comp.) PLA % 100 80 80 80 80 80 80 80 A% 0 0 2 4 6 10 15 20 B % 0 20 18 16 14 10 5 0 %A/%(A+B) 0,1 0,2 0,3 0,5 0,75 1 Choc 3,8 6,5 16,1 20,9 21,4 24,5 20,7 16,6 Charpy à 23 C (kJ/m2) Choc 3,7 5 5, 1 5,6 5 3,8 3,9 3,2 Charpy à - 40 C (kJ/m2) MFI 2,9 2,4 1,9 1,9 1,7 1,05 1, 4 1,0 -L'essai 1 montre clairement que le PLA est un matériau fragile nécessitant un renforcement au choc. Il sert de référence. - L'essai 2 montre que sans le composé A, le niveau de 15 renforcement reste faible, notamment à 23 C. - Les essais comparatifs 6 à 8 correspondent à l'invention divulguée dans WO 2005/059031. De telles compositions renfermant majoritairement du composé A conduisent à un renforcement aux chocs satisfaisant à 23 C. En revanche, on n'observe aucune amélioration de la résistance aux chocs à -40 C, voire une légère fragilisation lorsque le composé A est utilisé seul. - Les essais 3, 4 et 5 correspondent à l'invention De telles compositions renfermant plus de 50 % de composé B dans le mélange A +B conduisent à d'excellentes résistances aux chocs à 23 C ainsi qu'à -40 C. De plus, ces compositions permettent de conserver une bonne fluidité. lo  lo Table 1 Test 1 2 3 4 5 6 7 8 (ref) (comp.) (inv.) (inv.) (inv.) (comp.) (comp.) (comp.) PLA% 100 80 80 80 80 80 80 80 A% 0 0 2 4 6 10 15 20 B% 0 20 18 16 14 10 5 0% A /% (A + B) 0.1 0.2 0.3 0.5 0.75 1 Shock 3 , 8 6.5 16.1 20.9 21.4 24.5 20.7 16.6 Charpy at 23 C (kJ / m2) Shock 3.7 5 5, 1 5.6 5 3.8 3.9 3.2 Charpy at -40 C (kJ / m2) MFI 2.9 2.4 1.9 1.9 1.7 1.05 1, 4 1.0 -Test 1 clearly shows that PLA is a fragile material requiring impact reinforcement. It serves as a reference. Test 2 shows that without compound A, the level of reinforcement remains low, especially at 23 ° C. Comparative tests 6 to 8 correspond to the invention disclosed in WO 2005/059031. Such compositions containing predominantly compound A lead to impact strengthening satisfactory 23 C. However, there is no improvement in impact resistance at -40 C, or even a slight embrittlement when compound A is used alone. Tests 3, 4 and 5 correspond to the invention. Such compositions containing more than 50% of compound B in the A + B mixture lead to excellent impact strengths at 23 ° C. and -40 ° C. Moreover, these compositions make it possible to maintain a good fluidity. lo

Claims (10)

Revendicationsclaims 1. Composition d'acide polylactique comprenant en poids: - 60 à 97 % d'acide polylactique (PLA) et, - 3 à 40 % d'un mélange de composés A et B dans lequel, o A est un copolymère d'éthylène et d'un monomère insaturé porteur d'au moins une fonction époxyde ou acide carboxylique ou anhydride d'acide carboxylique, et éventuellement de (méth)acrylate d'alkyle. o B est un copolymère d'éthylène et de (méth)acrylate d'alkyle. le dit mélange présentant un rapport % poids (A) / (% poids (A +B)) compris entre 0,10 et 0,49. 15  A polylactic acid composition comprising by weight: 60 to 97% of polylactic acid (PLA) and 3-40% of a mixture of compounds A and B in which A is a copolymer of ethylene and an unsaturated monomer bearing at least one epoxide or carboxylic acid or carboxylic acid anhydride function, and optionally alkyl (meth) acrylate. B is a copolymer of ethylene and alkyl (meth) acrylate. said mixture having a ratio by weight (A) / (% by weight (A + B)) of between 0.10 and 0.49. 15 2. Composition selon la revendication 1, caractérisée en ce que A est choisi parmi le terpolymère éthylène-(méth)acrylate d'alkyle- anhydride maléique et le terpolymère éthylène-(méth)acrylate d'alkyle-méthacrylate de glycidyle.  2. Composition according to claim 1, characterized in that A is chosen from the ethylene-alkyl (meth) acrylate-maleic anhydride terpolymer and the ethylene-alkyl (meth) acrylate-glycidyl methacrylate terpolymer. 3. Composition selon l'une quelconque des revendications précédentes, 20 caractérisée en ce que A est un copolymère de l'éthylène, de l'acrylate de méthyle et du méthacrylate de glycidyle.  3. A composition as claimed in any one of the preceding claims, characterized in that A is a copolymer of ethylene, methyl acrylate and glycidyl methacrylate. 4. Composition selon l'une des revendications précédentes, caractérisée en ce que B est un copolymère de l'éthylène et de l'acrylate de méthyle, 25 d'éthyle, de n-butyle, d'isobutyle, de n-octyle ou de 2-éthylhexyle.  4. Composition according to one of the preceding claims, characterized in that B is a copolymer of ethylene and of methyl acrylate, ethyl, n-butyl, isobutyl, n-octyl or 2-ethylhexyl. 5. Composition selon l'une des revendications précédentes, caractérisée en ce que le rapport % poids (A) / (% poids (A +B)) du mélange est compris entre 0,15 et 0,40, et préférentiellement entre 0,20 et 0,30. l0 30  5. Composition according to one of the preceding claims, characterized in that the ratio by weight (A) / (% by weight (A + B)) of the mixture is between 0.15 and 0.40, and preferably between 0, 20 and 0.30. l0 30 6. Procédé de préparation de la composition selon l'une quelconque des revendications précédentes dans lequel on réalise par extrusion le mélange simultané du PLA, de A et de B.  6. Process for the preparation of the composition according to any one of the preceding claims, in which the simultaneous mixing of PLA, A and B is carried out by extrusion. 7. Procédé de préparation de la composition selon l'une des revendications 1 à 5, dans lequel on réalise par extrusion: - dans une première étape le mélange par extrusion de A et B puis, - dans une seconde étape le mélange par extrusion du produit issu de la première étape avec le PLA.  7. Process for the preparation of the composition according to one of claims 1 to 5, wherein is carried out by extrusion: in a first step the mixture by extrusion of A and B and in a second step the mixture by extrusion of product from the first stage with PLA. 8. Pièce ou objet obtenu à partir de la composition selon l'une des revendications 1 à 5, caractérisée en ce que la pièce ou objet est réalisé par un procédé choisi parmi le moulage, l'extrusion, et le thermoformage.  8. Part or object obtained from the composition according to one of claims 1 to 5, characterized in that the part or object is made by a method selected from molding, extrusion, and thermoforming. 9. Pièce ou objet selon la revendication 8, dont la réalisation comprend en outre une étape de recuit.  9. Part or object according to claim 8, the embodiment of which further comprises an annealing step. 10. Structure multicouche comprenant une couche de la composition selon 20 l'une des revendications 1 à 5 et au moins une couche d'un thermoplastique choisi parmi le polyéthylène (PE), le polypropylène (PP), le polystyrène (PS), le polyamide (PA) et le copolymère éthylène / alcool vinylique (EVOH). lo '5  10. A multilayer structure comprising a layer of the composition according to one of claims 1 to 5 and at least one layer of a thermoplastic selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), polyamide (PA) and the ethylene / vinyl alcohol copolymer (EVOH). lo '5
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ES07788972T ES2368093T3 (en) 2006-06-16 2007-06-11 COMPOSITION OF LACTIC POLYACCID THAT PRESENTS AN IMPACT IMPACT RESISTANCE.
CN2007800279732A CN101495568B (en) 2006-06-16 2007-06-11 Poly(lactic acid) composition with improved impact resistance
US12/305,127 US9512311B2 (en) 2006-06-16 2007-06-11 Poly(lactic acid) composition with improved impact resistance
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AT07788972T ATE518912T1 (en) 2006-06-16 2007-06-11 POLY(LACTIC ACID) COMPOSITION WITH IMPROVED IMPACT RESISTANCE
JP2009514857A JP5174017B2 (en) 2006-06-16 2007-06-11 Polylactic acid composition with improved impact resistance
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